CN108428888B - Spherical surface compact nickel-cobalt-aluminum ternary material, precursor thereof, preparation method and application thereof - Google Patents
Spherical surface compact nickel-cobalt-aluminum ternary material, precursor thereof, preparation method and application thereof Download PDFInfo
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a spherical surface compact nickel-cobalt-aluminum ternary material, a precursor thereof, a preparation method and application thereof. The preparation method of the nickel-cobalt-aluminum ternary material precursor comprises the following steps: dissolving a nickel source, a cobalt source and an aluminum source compound in deionized water to prepare a solution; then mixing the prepared solution with a complexing agent, and then enabling the mixed solution to flow into a reaction kettle in parallel with a precipitator and an additive for reaction; then carrying out post-treatment on the obtained precursor slurry of the nickel-cobalt-aluminum ternary material to obtain a spherical nickel-cobalt-aluminum ternary material precursor Ni with a compact surface0.8Co0.15Al0.05(OH)2. The nickel-cobalt-aluminum ternary material precursor prepared by the method is a single substance (not a mixture of multiple substances), has good product crystallinity, is regular spherical or spheroidal in product appearance and compact in spherical surface, and can be used for preparing a lithium ion battery anode material-nickel-cobalt-aluminum lithium with better performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery preparation, and particularly relates to a method for preparing a spherical and compact nickel-cobalt-aluminum ternary material precursor by a metal ion coprecipitation process in a liquid phase system, high-density nickel-cobalt lithium aluminate prepared by the method, a positive electrode material taking the nickel-cobalt lithium aluminate as a main body and a secondary battery containing the positive electrode material.
Background
Lithium ion batteries are widely used because of their advantages of large capacity, high rate capability, good safety, and low price. Li [ Ni ]1-xMx]O2The (M ═ Co, Mn, Al and the like) high nickel material is a lithium battery positive electrode material with the most promising prospect due to the specific capacity of 200 mAh/g. Wherein LiNi0.8Co0.15Al0.05O2Due to the addition of Co and Al, the stability of the structure is enhanced, and more excellent electrochemical performance is shown. However, in order to increase the tap density of a material and further increase the volumetric energy density of the material, LiNi has been used in the prior art0.8Co0.15Al0.05O2The material is mostly made into large-diameter spherical particles.
For the research of the ternary material nickel, cobalt and aluminum, the emphasis of the surrounding whether in foreign countries or in China is mostly on improving the compaction density and the circulation rate of the ternary material. Taking the Tesla company as an example, a cylindrical 18650 type lithium ion battery prepared by taking NCA as a positive electrode material is adopted in a second type of mass-produced Model-S, a 18650 battery with 2.9AH is adopted in the early Model-S, a battery with 3.1AH is improved in the later stage, and a ternary 18650 battery of a new energy automobile which is mainstream in China at the same time is 2.2-2.6 AH. The Model 3 adopts a nickel-cobalt-aluminum 20700 battery, the battery has larger breakthrough in diameter and height, the energy density of the monomer can reach 343Wh/Kg, the capacity of the battery cell can reach 6.2AH, and the integral improvement is doubled compared with the 3.1AH capacity of the prior 18650 battery. With the success of Tesla corporation, domestic battery material manufacturers have also begun to perform NCA material research, development and production in many cases. CGII research has shown that domestic enterprises engaged in NCA materials business (without research institutions) exceed 15 but have major shortcomings with respect to the market demand for NCA materials due to late initiatives.
Under the situation that the endurance mileage of new energy vehicles is required to be continuously increased, the cathode material which has a decisive influence on the energy density of the power battery is developing towards high nickel, and the NCA material which is loosened to be successfully applied in a large scale is the most feasible technical scheme at present, and even possibly occupies the market leading position of the new energy passenger vehicle power battery in the future. The NCA material has high gram capacity, is similar to NCM811 type ternary, has a compaction density close to NCM 532 type ternary, and integrates LiNiO2And LiCoO2The aluminum-doped titanium-based composite material has the advantages of high reversible specific capacity, and meanwhile, the structural stability and safety of the material are enhanced after the aluminum element is doped, so that the cyclicity of the material is improved. Therefore, the NCA material has become one of the most popular materials in current commercial cathode materials.
Upon search, numerous patents have been published on the preparation of NCA materials and their precursors. For example, the application with chinese patent application No. 201510988534.4 discloses a method for preparing a nickel-cobalt-aluminum oxide with an ultra-large particle size, which selects soluble nickel salt, cobalt salt and aluminum salt as raw materials to prepare a nickel-cobalt-aluminum solution, and causes the nickel-cobalt-aluminum solution, a sodium hydroxide precipitant, and a mixed complexing agent consisting of ammonia water and ammonium salt water to flow in parallel into a reaction kettle for reaction, so as to prepare a nickel-cobalt-aluminum hydroxide synthesis slurry, and then the synthesis slurry is subjected to subsequent treatment and calcination to obtain the nickel-cobalt-aluminum oxide with the ultra-large particle size. For another example, chinese patent application No. 201510233112.6 discloses a method for preparing a nickel-cobalt-aluminum precursor material and a positive electrode material having a gradient distribution of aluminum elements, the method including the steps of: preparing a nickel cobalt salt aqueous solution mixed by nickel salt and cobalt salt, a solution containing a complexing agent I, a solution containing a complexing agent II and a sodium hydroxide solution, and mixing aluminum salt and the complexing agent I to prepare an aluminum-containing complexing solution; adding a base solution containing the complexing agent II into a reaction kettle in advance; adding the nickel-cobalt-aluminum aqueous solution, the solution containing the complexing agent I, the solution containing the complexing agent II, the solution containing the aluminum complexing agent and the sodium hydroxide solution into the reaction kettle which is continuously stirred for precipitation reaction to obtain the precursor material, wherein the complexing agent I is one or more of triethanolamine, ammonium fluoride, citric acid, oxalic acid, sodium ethylene diamine tetracetate and sodium hydroxide, and the complexing agent II is one or more of ammonia water, triethanolamine, ammonium fluoride, citric acid, oxalic acid and sodium ethylene diamine tetracetate. However, the cycle performance of the nickel-cobalt-aluminum ternary material precursor prepared by the above application still needs to be further improved.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to overcome the problems in the prior art and provides a spherical surface compact nickel-cobalt-aluminum ternary material, a precursor thereof, a preparation method and application thereof. The preparation method can be used for preparing a single (non-mixture of various substances), nickel-cobalt-aluminum ternary material precursor with good product crystallinity, regular spherical or spherical-like particle morphology and compact surface, and the precursor can be used for preparing a nickel-cobalt-lithium aluminate ternary cathode material with better performance.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the preparation method of the spherical surface compact nickel-cobalt-aluminum ternary material precursor adopts a process of coprecipitation of metal ions and nonmetal materials in a deionized water system, and specifically comprises the following steps:
1) weighing soluble nickel source, cobalt source and aluminum source compounds according to the molar ratio of Ni/Co/Al of 80:15:5, and dissolving the nickel source, cobalt source and aluminum source compounds in deionized water to prepare a solution with a certain concentration;
2) controlling the temperature of a reaction system at 25-85 ℃, uniformly mixing the prepared solution and a complexing agent, allowing the solution and a precipitator to flow in parallel into a reaction kettle containing a base solution under stirring, and adding an additive for reaction to obtain precursor slurry of the nickel-cobalt-aluminum ternary material;
3) washing, filtering, repulping and spray drying the obtained nickel-cobalt-aluminum ternary material precursor slurry to obtain the spherical nickel-cobalt-aluminum ternary material precursor Ni with compact surface0.8Co0.15Al0.05(OH)2And (5) producing the product.
Furthermore, the pH value in the reaction kettle is controlled to be 8-12, and after the pH value of the reaction system is stable, the reaction is continued for 6-24 hours.
Furthermore, the weight ratio of the deionized water, the nickel source, the cobalt source and the aluminum source in the step 1) is 100: (10-60): (2-15): (1-2).
Furthermore, the base solution is one or more of sodium benzene sulfonate, sodium dodecyl sulfate, sodium lignin sulfonate, sulfamic acid and sodium alkyl benzene sulfonate, and the addition amount of the base solution is 0.01-0.05% of the total weight of the reaction solution.
Furthermore, the complexing agent is one or more of ammonia water, ammonium sulfate, ammonium chloride and ammonium nitrate, and the mol sum of Ni, Co and Al metal ions and NH in the solution after the complexing agent is added4 +The ratio of the number of moles of (a) is 0.8 to 2.0; the precipitator is one or more of ammonia water, sodium hydroxide, potassium hydroxide, zinc hydroxide and aluminum hydroxide solution, and the concentration of the precipitator is 2.5-6 mol/L.
Furthermore, the additive is one or more of citric acid, glucose, SIMULSOL SL 8, sodium lignosulfonate and calcium lignosulfonate, and the dosage of the additive is 0.2-5% of the total amount of the sample.
Furthermore, the soluble nickel source compound is one or more of nickel sulfate, nickel dichloride and nickel nitrate, the soluble cobalt source compound is one or more of cobalt nitrate, cobalt sulfate, cobalt oxalate and cobalt dichloride, the soluble aluminum source compound is one or more of aluminum nitrate, aluminum sulfate, sodium tetrahydroxyaluminate and sodium metaaluminate, the concentration of nickel in the solution obtained in the step 1) is 25-150 g/L, the concentration of cobalt is 5-25 g/L, and the concentration of aluminum is 2-8 g/L.
Secondly, the precursor of the spherical surface compact nickel-cobalt-aluminum ternary material is a regular spherical or spheroidal compact particle structure, the particle size D50 of the precursor is 8-12 mu m, and the specific surface area of the precursor is not more than 10m2/g。
Thirdly, the spherical surface compact nickel-cobalt-aluminum ternary material is synthesized by the precursor of the nickel-cobalt-aluminum ternary material prepared according to any one of claims 2 to 8 and a lithium compound, and the specific capacity retention rate of the obtained nickel-cobalt-lithium aluminate product after 500 times of cyclic discharge under the conditions of voltage range of 2.7-4.2V and high rate discharge of 1C is as high as about 90%.
Fourthly, the secondary battery comprises the positive electrode made of the nickel-cobalt lithium aluminate positive electrode material.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) the precursor of the nickel-cobalt-aluminum ternary material with the spherical surface is a regular spherical or spheroidal compact particle structure, the particle size D50 of the precursor is 8-12 mu m, the particle size distribution is narrow, and the specific surface area is not more than 20m2The nickel cobalt lithium aluminate anode material prepared from the precursor has excellent cycle performance.
(2) The preparation method of the spherical surface compact nickel-cobalt-aluminum ternary material precursor adopts a process of coprecipitation of metal ions and nonmetal materials in a deionized water system, and controls the coprecipitation process of nickel-cobalt-aluminum hydroxide by controlling reaction conditions, so that the regular spherical or sphere-like nickel-cobalt-aluminum ternary material precursor can be prepared, and the particle surface of the obtained precursor product is compact and has good cycle performance.
(3) According to the preparation method of the spherical surface compact nickel-cobalt-aluminum ternary material precursor, the specific additive is added into the reaction kettle and the specific primer solution is matched, so that the particle surface appearance and the particle size of the obtained product are further changed, the particle surface is more compact, the particles grow up further, the changes effectively improve the cycle performance of the anode material prepared from the obtained product, the cycle retention rate of the NCA ternary material obtained by firing for 50 times is kept above 90%, the change of the particle surface can reduce the reaction activity of the material, and the safety of the material is improved.
(4) The preparation method of the spherical surface compact nickel-cobalt-aluminum ternary material precursor can effectively ensure that the content of Ni in the obtained product is 53.23-56.20%, the content of Co is 9.65-10.96%, the content of Al is 1.35-1.51%, the content of S is 0.026-0.065%, the product has good crystallinity and high purity, the granularity D50 is about 12 mu m, the granularity distribution is narrow, and the specific surface area is not more than 20m2/g。
(5) The spherical surface compact nickel-cobalt-aluminum ternary material is synthesized by the precursor prepared by the method and a lithium compound, can keep the compact spherical shape of the surface of the precursor, shows that the product is basically free of impure phases through XRD analysis, has a specific capacity retention rate of about 90 percent after 500 times of cyclic discharge under the conditions of a voltage range of 2.7-4.2V and 1C high-rate discharge, and has excellent cycle performance and safety performance. The battery anode made of the nickel-cobalt-aluminum ternary material is applied to a secondary battery, and a high-capacity and high-power secondary battery with good safety can be obtained.
Drawings
FIG. 1 is an XRD pattern of nickel cobalt aluminum hydroxide obtained in example 1;
FIG. 2 is an SEM photograph of the nickel cobalt aluminum hydroxide obtained in example 1;
FIG. 3 is a high-magnification SEM image of Ni-Co-Al hydroxide obtained in example 1;
fig. 4 is an SEM image of the nickel cobalt aluminum hydroxide obtained in comparative example 1.
Detailed Description
The preparation method of the spherical surface compact nickel-cobalt-aluminum ternary material precursor (nickel-cobalt-aluminum hydroxide) comprises the following steps: 1) weighing soluble nickel source, cobalt source and aluminum source compounds according to the molar ratio of Ni/Co/Al of 80:15:5, and dissolving the nickel source, cobalt source and aluminum source compounds in deionized water to prepare a solution with a certain concentration; 2) and mixing the prepared solution with a complexing agent according to the molar sum of the metal elements: NH (NH)4 +Mixing the solution and a prepared precipitator according to a molar ratio of 0.8-2.0, uniformly stirring, then enabling the solution and the prepared precipitator to flow into a reaction kettle which is in a stirring state and is added with a base solution, controlling the temperature of a reaction system to be 25-85 ℃, simultaneously adding an additive, controlling the pH value in the reaction kettle to be 8-12, and continuing to react for 6-24 hours after the pH value of the reaction system is stable; 3) washing, filtering, repulping and spray drying the obtained precursor slurry of the nickel-cobalt-aluminum ternary material to obtain a spherical and compact precursor Ni of the nickel-cobalt-aluminum ternary material0.8Co0.15Al0.05(OH)2And (5) producing the product.
The soluble nickel source compound is one or more of nickel sulfate, nickel dichloride and nickel nitrate, the soluble cobalt source compound is one or more of cobalt nitrate, cobalt sulfate, cobalt oxalate and cobalt dichloride, the soluble aluminum source compound is one or more of aluminum nitrate, aluminum sulfate, sodium tetrahydroxyaluminate, aluminum chloride and sodium metaaluminate, the concentration of nickel in the solution obtained in the step 1) is 25-150 g/L, the concentration of cobalt is 5-25 g/L, and the concentration of aluminum is 2-8 g/L. The precipitator is one or more of ammonia water, sodium hydroxide, potassium hydroxide, zinc hydroxide and aluminum hydroxide, and the concentration of the precipitator is 2.5-6 mol/L; the complexing agent is one or more of ammonia water, ammonium sulfate, ammonium chloride and ammonium nitrate, and the dosage of the complexing agent is determined according to the solutionThe sum of the metal ion moles and a complexing agent NH4 +The molar ratio of (a) to (b) is 0.8 to 2.0. The additive is one or more of citric acid, glucose, SIMULSOL SL 8, sodium lignosulfonate and calcium lignosulfonate, and the dosage of the additive is 0.2-5% of the total amount of a sample; the base solution is one or more of sodium benzene sulfonate, sodium dodecyl sulfonate, sodium lignin sulfonate, sulfamic acid and sodium alkyl benzene sulfonate, and the addition amount of the base solution is 0.01-0.05% of the total weight of the reaction solution.
The invention adopts the process that a complexing agent is uniformly mixed with a reaction raw material solution and then is coprecipitated with a precipitator under a certain pH value to prepare a nickel-cobalt-aluminum ternary material precursor; controlling the pH value of the reaction system by controlling the adding speed of the precipitator; the proportional relation between the three main elements of Ni, Co and Al and the precipitant is controlled by controlling the adding speed of the mixed solution, and the granularity and the appearance of the product are controlled by controlling the adding amount of the additive, so that the coprecipitation process of the three main elements of nickel, cobalt and aluminum is finally controlled. According to the invention, a certain additive is added into the reaction kettle, and a specific substance is adopted as a reaction base solution, so that the surface appearance and the particle size of the obtained product can be effectively controlled, and the precursor Ni is enabled to be Ni0.8Co0.15Al0.05(OH)2The particle surface of the product is more compact, the particles grow further, and the particles and a lithium compound are calcined at high temperature, so that high-purity nickel cobalt lithium aluminate suitable for an electrode active substance for a secondary battery can be obtained, and the cycle performance and the safety performance of the prepared nickel cobalt lithium aluminate product are improved. The lithium compound is a common lithium compound prepared by the prior nickel cobalt lithium aluminate, such as Li (CH)3COO)·2H2O、LiOH·H2O、Li2CO3And so on.
The nickel cobalt lithium aluminate is used as a main body, a secondary battery anode material which is safe and has high energy density can be manufactured, and a battery anode which is manufactured by the battery anode material can be applied to a secondary battery, so that a secondary battery with high capacity and high power and good safety can be obtained.
For a further understanding of the invention, reference will now be made in detail to specific embodiments of the invention.
Example 1
Weighing 100.00g of nickel sulfate, 20.06g of cobalt sulfate and 7.92g of aluminum sulfate according to the molar ratio of Ni/Co/Al of 80:15:5, and dissolving the nickel sulfate, the cobalt sulfate and the aluminum sulfate in deionized water to prepare a mixed solution with the total metal ion concentration of 1 mol/L; according to the sum of the metal element moles and NH4 +Adding 73.1mL of 25% ammonia water into the mixed solution with the molar ratio of 1.0; controlling the temperature of a reaction system at 60 ℃, enabling the prepared solution and a prepared NaOH solution with 5mol/L of precipitator to flow in parallel into a reaction kettle in a stirring state, adding sodium benzenesulfonate serving as a base solution into the reaction kettle, wherein the amount of the sodium benzenesulfonate is 0.01 percent of the total weight of the reaction solution; then adding 1.5g of additive (SIMULSOL SL 8) and controlling the pH value in the reaction kettle to be 11.0; after the pH value of the reaction system is stable, continuing to react for 8 hours; then washing, filtering, repulping and spray drying the obtained precursor slurry of the nickel-cobalt-aluminum ternary material to obtain a spherical and compact nickel-cobalt-aluminum ternary material precursor Ni0.8Co0.15Al0.05(OH)2And (5) producing the product. With reference to FIGS. 1-3, the precursor Ni prepared in this example0.8Co0.15Al0.05(OH)2The product has basically no impure phase, high purity and Ni0.8Co0.15Al0.05(OH)2The surface of the product is compact.
Comparative example 1
Weighing 100.00g of nickel sulfate, 20.06g of cobalt sulfate and 7.92g of aluminum sulfate according to the molar ratio of Ni/Co/Al of 80:15:5, and dissolving the nickel sulfate, the cobalt sulfate and the aluminum sulfate in deionized water to prepare a mixed solution with the total metal ion concentration of 1 mol/L; controlling the temperature of a reaction system at 60 ℃, enabling the prepared mixed solution, 73.1mL of strong ammonia water with a complexing agent mass fraction of 25% and a prepared NaOH solution with a precipitator mass fraction of 5mol/L to flow into a reaction kettle in a stirring state in parallel, and controlling the pH value in the reaction kettle to be 11.0; after the pH value of the reaction system is stable, continuing to react for 8 hours; then washing, filtering and drying the obtained precursor slurry of the nickel-cobalt-aluminum ternary material to obtain the nickel-cobalt-aluminum ternary material precursorBulk Ni0.8Co0.15Al0.05(OH)2The product, with reference to fig. 4, has an irregular blocky structure and relatively poor cycle rate performance.
Example 2
Weighing 100.00g of nickel chloride, 18.76g of cobalt chloride and 3.51g of aluminum chloride according to the molar ratio of Ni/Co/Al of 80:15:5, and dissolving the nickel chloride, the cobalt chloride and the aluminum chloride in deionized water to prepare a mixed solution with the total metal ion concentration of 2 mol/L; according to the sum of the metal element moles and NH4 +Adding 18.76g of ammonium chloride into the mixed solution with the molar ratio of 1.5; controlling the temperature of a reaction system at 55 ℃, enabling the prepared solution and a prepared KOH solution of 2.5mol/L of precipitator to flow in parallel into a reaction kettle in a stirring state, wherein the reaction kettle contains sodium dodecyl sulfate as a base solution, and the addition amount of the sodium dodecyl sulfate is 0.03 percent of the total weight of the reaction solution; then adding 1.5g of additive sodium lignosulphonate, and controlling the pH value in the reaction kettle to be 10.5; after the pH value of the reaction system is stable, continuing to react for 6 hours; then washing, filtering, repulping and spray drying the obtained precursor slurry of the nickel-cobalt-aluminum ternary material to obtain a spherical and compact nickel-cobalt-aluminum ternary material precursor Ni0.8Co0.15Al0.05(OH)2And (5) producing the product.
Example 3
Weighing 100.00g of nickel nitrate, 18.76g of cobalt nitrate and 8.06g of aluminum nitrate according to the molar ratio of Ni/Co/Al of 80:15:5, and dissolving the nickel nitrate, the cobalt nitrate and the aluminum nitrate in deionized water to prepare a mixed solution with the total metal ion concentration of 1 mol/L; according to the sum of the metal element moles and NH4 +113.0g of ammonium sulfate was added to the mixed solution at a molar ratio of 0.8; controlling the temperature of a reaction system at 65 ℃, enabling the prepared solution and a prepared 6mol/L NaOH solution of a precipitator to flow in parallel into a reaction kettle in a stirring state, enabling the reaction kettle to contain sodium lignosulfonate as a base solution, adding 0.05% of the sodium lignosulfonate by weight of the reaction solution, then adding 2.0g of additive calcium lignosulfonate, and controlling the pH value in the reaction kettle to be 11.2; after the pH value of the reaction system is stable, continuing to react for 7 hours; then washing, filtering and purifying the obtained precursor slurry of the nickel-cobalt-aluminum ternary material,Then the mixture is pulped and spray-dried to obtain a spherical and compact nickel-cobalt-aluminum ternary material precursor Ni0.8Co0.15Al0.05(OH)2And (5) producing the product.
Example 4
Weighing 100.00g of nickel chloride, 18.76g of cobalt chloride and 2.16g of sodium metaaluminate according to the molar ratio of Ni/Co/Al of 80:15:5, and dissolving the nickel chloride, the cobalt chloride and the sodium metaaluminate in deionized water to prepare a mixed solution with the total metal ion concentration of 2.5 mol/L; according to the sum of the metal element moles and NH4 +Adding 81.0mL of 25% ammonia water into the mixed solution with the molar ratio of 1.0; controlling the temperature of a reaction system at 70 ℃, enabling the prepared solution and a prepared KOH solution with 4mol/L of precipitator to flow into a reaction kettle in a stirring state in parallel, enabling the reaction kettle to contain sulfamic acid as a base solution, adding 0.02 percent of additive (SIMULSOL SL 8) by weight of the total weight of the reaction solution, then adding 2.0g of additive (SIMULSOL SL 8), and controlling the pH value in the reaction kettle at 10.8; after the pH value of the reaction system is stable, continuing the reaction for 9 hours; then washing, filtering, repulping and spray drying the obtained precursor slurry of the nickel-cobalt-aluminum ternary material to obtain a spherical and compact nickel-cobalt-aluminum ternary material precursor Ni0.8Co0.15Al0.05(OH)2And (5) producing the product.
Example 5
Weighing 100.00g of nickel sulfate, 20.06g of cobalt sulfate and 1.95g of sodium metaaluminate according to the molar ratio of Ni/Co/Al of 80:15:5, and dissolving the nickel sulfate, the cobalt sulfate and the sodium metaaluminate in deionized water to prepare a mixed solution with the total metal ion concentration of 0.8 mol/L; according to the sum of the metal element moles and NH4 +Adding 40.0g of ammonium nitrate into the mixed solution with the molar ratio of 0.95; controlling the temperature of a reaction system at 65 ℃, enabling the prepared solution and a prepared 6mol/L NaOH solution of a precipitator to flow in parallel into a reaction kettle in a stirring state, enabling the reaction kettle to contain sodium alkyl benzene sulfonate as a base solution, adding 0.04% of sodium lignosulfonate as an additive, adding 1.5g of sodium lignosulfonate as an additive, and controlling the pH value in the reaction kettle to be 11.2; after the pH value of the reaction system is stable, continuing to react for 8 hours; then washing and passing the obtained precursor slurry of the nickel-cobalt-aluminum ternary materialFiltering, repulping and spray drying to obtain a spherical and compact nickel-cobalt-aluminum ternary material precursor Ni0.8Co0.15Al0.05(OH)2And (5) producing the product.
Example 6
Weighing 100.00g of nickel sulfate, 20.06g of cobalt sulfate and 1.95g of sodium metaaluminate according to the molar ratio of Ni/Co/Al of 80:15:5, and dissolving the nickel sulfate, the cobalt sulfate and the sodium metaaluminate in deionized water to prepare a mixed solution with the total metal ion concentration of 0.8 mol/L; according to the sum of the metal element moles and NH4 +Adding 40.0g of ammonium nitrate into the mixed solution with the molar ratio of 2.0; controlling the temperature of a reaction system at 85 ℃, enabling the prepared solution and a prepared 6mol/L NaOH solution of a precipitator to flow in parallel into a reaction kettle in a stirring state, enabling a mixed solution containing sodium benzenesulfonate and sodium dodecyl sulfate in the reaction kettle to serve as a base solution, adding 1.5g of additive citric acid, wherein the added amount of the mixed solution is 0.05 percent of the total weight of the reaction solution, and controlling the pH value in the reaction kettle to be 8.2; after the pH value of the reaction system is stable, continuing the reaction for 15 h; then washing, filtering, repulping and spray drying the obtained precursor slurry of the nickel-cobalt-aluminum ternary material to obtain a spherical and compact nickel-cobalt-aluminum ternary material precursor Ni0.8Co0.15Al0.05(OH)2And (5) producing the product.
Example 7
Weighing nickel sulfate (100.00g), cobalt oxalate and sodium tetrahydroxy aluminate according to the molar ratio of Ni/Co/Al of 80:15:5, and dissolving the nickel sulfate, the cobalt oxalate and the sodium tetrahydroxy aluminate in deionized water to prepare a mixed solution with the total metal ion concentration of 0.9 mol/L; according to the sum of the metal element moles and NH4 +Adding 40.0g of ammonium nitrate into the mixed solution with the molar ratio of 0.95; controlling the temperature of a reaction system at 25 ℃, enabling the prepared solution and a prepared 6mol/L NaOH solution of a precipitator to flow in parallel into a reaction kettle in a stirring state, taking a mixed solution containing sodium lignosulfonate, sulfamic acid and sodium alkyl benzene sulfonate in the reaction kettle as a base solution, and adding 0.01-0.05% of the total weight of the reaction solution of the base solution; then adding 1.7g of additive glucose, and controlling the pH value in the reaction kettle to be 9.7; after the pH value of the reaction system is stable, continuing to reactReacting for 24 hours; then washing, filtering, repulping and spray drying the obtained precursor slurry of the nickel-cobalt-aluminum ternary material to obtain a spherical and compact nickel-cobalt-aluminum ternary material precursor Ni0.8Co0.15Al0.05(OH)2And (5) producing the product.
Example 8
Weighing 100.00g of nickel sulfate, 20.06g of cobalt sulfate and 1.95g of sodium metaaluminate according to the molar ratio of Ni/Co/Al of 80:15:5, and dissolving the nickel sulfate, the cobalt sulfate and the sodium metaaluminate in deionized water to prepare a mixed solution with the total metal ion concentration of 0.8 mol/L; according to the sum of the metal element moles and NH4 +Adding 40.0g of ammonium nitrate into the mixed solution with the molar ratio of 0.95; controlling the temperature of a reaction system at 45 ℃, enabling the prepared solution and a prepared 6mol/L NaOH solution of a precipitator to flow in parallel into a reaction kettle in a stirring state, enabling the reaction kettle to contain sodium lignosulfonate as a base solution, adding 0.01-0.05% of the base solution by weight of the reaction solution, adding 1.5g of a mixture of an additive SIMULSOL SL 8 and the sodium lignosulfonate, and controlling the pH value in the reaction kettle to be 12; after the pH value of the reaction system is stable, continuing the reaction for 12 hours; then washing, filtering, repulping and spray drying the obtained precursor slurry of the nickel-cobalt-aluminum ternary material to obtain a spherical and compact nickel-cobalt-aluminum ternary material precursor Ni0.8Co0.15Al0.05(OH)2And (5) producing the product.
Claims (8)
1. A preparation method of a spherical surface compact nickel-cobalt-aluminum ternary material precursor is characterized by comprising the following steps:
1) weighing soluble nickel source, cobalt source and aluminum source compounds according to the molar ratio of Ni/Co/Al of 80:15:5, and dissolving the nickel source, cobalt source and aluminum source compounds in deionized water to prepare a solution with a certain concentration;
2) controlling the temperature of a reaction system at 25-85 ℃, uniformly mixing the prepared solution and a complexing agent, allowing the solution and a precipitator to flow in parallel into a reaction kettle containing a base solution under stirring, and adding an additive for reaction to obtain precursor slurry of the nickel-cobalt-aluminum ternary material; the base solution is one or more of sodium benzene sulfonate, sodium dodecyl sulfate, sodium lignin sulfonate, sulfamic acid and sodium alkyl benzene sulfonate; the additive is one or more of citric acid, glucose, SIMULSOL SL 8, sodium lignosulfonate and calcium lignosulfonate; the addition amount of the base solution is 0.01-0.05% of the total weight of the reaction solution, and the dosage of the additive is 0.2-5% of the total weight of the sample;
3) washing, filtering, repulping and spray drying the obtained nickel-cobalt-aluminum ternary material precursor slurry to obtain the spherical nickel-cobalt-aluminum ternary material precursor Ni with compact surface0.8Co0.15Al0.05(OH)2And (5) producing the product.
2. The method for preparing the spherical surface compact nickel-cobalt-aluminum ternary material precursor according to claim 1, wherein the method comprises the following steps: and controlling the pH value in the reaction kettle to be 8-12, and continuing to react for 6-24 hours after the pH value of the reaction system is stable.
3. The method for preparing the spherical surface compact nickel-cobalt-aluminum ternary material precursor according to claim 1, wherein the method comprises the following steps: the weight ratio of the deionized water, the nickel source, the cobalt source and the aluminum source in the step 1) is 100: (10-60): (2-15): (1-2).
4. The method for preparing the spherical surface compact nickel-cobalt-aluminum ternary material precursor according to any one of claims 1 to 3, wherein the method comprises the following steps: the complexing agent is one or more of ammonia water, ammonium sulfate, ammonium chloride and ammonium nitrate, and the mol sum of Ni, Co and Al metal ions and NH in the solution after the complexing agent is added4 +The ratio of the number of moles of (a) is 0.8 to 2.0; the precipitator is one or more of ammonia water, sodium hydroxide, potassium hydroxide, zinc hydroxide and aluminum hydroxide solution, and the concentration of the precipitator is 2.5-6 mol/L.
5. The method for preparing the spherical surface compact nickel-cobalt-aluminum ternary material precursor according to any one of claims 1 to 3, wherein the method comprises the following steps: the method comprises the following steps of 1) preparing a solution containing nickel, cobalt, aluminum, cobalt sulfate, cobalt chloride, sodium tetrahydroxyaluminate and sodium metaaluminate, wherein the soluble nickel source compound is one or more of nickel sulfate, nickel dichloride and nickel nitrate, the soluble cobalt source compound is one or more of cobalt nitrate, cobalt sulfate, cobalt oxalate and cobalt dichloride, the soluble aluminum source compound is one or more of aluminum nitrate, aluminum sulfate, aluminum chloride, sodium tetrahydroxyaluminate and sodium metaaluminate, the concentration of nickel in the solution obtained in the step 1) is 25-150 g/L, the concentration of cobalt is 5-25 g/L, and the concentration of aluminum is 2-8 g/L.
6. A spherical surface compact nickel-cobalt-aluminum ternary material precursor prepared by the method of any one of claims 1 to 5, which is characterized in that: the nickel-cobalt-aluminum ternary material precursor is of a regular spherical or spheroidal compact particle structure, the particle size D50 is 8-12 mu m, and the specific surface area is not more than 10m2/g。
7. The spherical surface compact nickel-cobalt-aluminum ternary material is characterized in that: the ternary material is synthesized by the precursor of the nickel-cobalt-aluminum ternary material prepared by any one of claims 1-5 and a lithium compound, and the specific capacity retention rate of the obtained nickel-cobalt-lithium aluminate product after 500 times of cyclic discharge under the condition of high-rate discharge of voltage range 2.7-4.2V and 1C is as high as about 90%.
8. A secondary battery, characterized in that: the secondary battery includes a positive electrode made of the nickel-cobalt-aluminum ternary material according to claim 7.
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